DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Response to Amendments
Applicant’s amendments with respect to claims 1, 13, and 18, filed 06/02/2025, have been fully considered. No new matter is introduced by the amendments.
Response to Arguments
Applicant’s arguments regarding the previous 35 U.S.C. 102/103 rejections with respect and consideration of the amendments to claims 1, 13, and 18, filed 06/02/2025, have been fully considered and are persuasive. Therefore, the previous rejections have been withdrawn. However, upon further consideration, a new grounds of rejection is made, as necessitated by the claim amendments, in view of a new prior art reference: Paz de Araujo et al. (US 20170213961 A1), as further explained below.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 3, 5-8, 11, 13, 16, and 18-19 are rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1).
Regarding claim 1, Meyers et al. teaches “a method for forming a radiation patternable coating comprising a metal oxo-hydroxo network” (column 2, lines 63-65) where “the method comprising inputting into a deposition chamber closed from the ambient atmosphere separately a first precursor vapor comprising a compound RnSnX4-n where n=1 or 2, wherein R is a hydrocarbyl group with 1-31 carbon atoms, and X is a hydrolysable or oxidizable ligand and a second precursor vapor comprising an oxygen containing compound capable of hydrolyzing or oxidizing the first precursor vapor under conditions in the deposition chamber to form a hydrolyzed or oxidized composition” (column 2, line 67 and column 3, lines 1-8). The deposition chamber is under vacuum “generally from about 0.01 Torr to about 25 Torr” (column 19, lines 54-55) of pressure using “chemical vapor deposition (CVD)” (column 6, lines 9-10) resulting in “positive tone imaging” (column 23, line 11 and Figs. 5 and 6) and performing a “pre-patterning bake step” (column 5, line 46) wherein the metal-oxo coating is baked “in the presence of water, or another suitable source of oxygen and hydrogen” (column 7, lines 2-3).
Regarding claim 5, Meyers et al. teaches the method of claim 1, as explained above, and that the CVD process is thermal as “the substrate and/or chamber and/or vapors may be heated to promote reaction and deposition on the substrate surface” (column 19, lines 58-59).
Regarding claim 11, Meyers et al. teaches the method of claim 1, as explained above, that the tin (Sn) “compounds can hydrolyze on exposure to water vapor or hydroxide moieties, condensing with the initial organotin oxide hydroxides” (column 8, lines 19-21) and the CVD is a condensation process where “if the hydrolysis takes place during a continuous deposition process, it can be considered a CVD process” (column 6, lines 19-21).
Regarding claim 13, Meyers et al. teaches the method of forming a photoresist layer, as explained above under claim 1, and the deposition method is “atomic layer deposition (ALD)” (column 6, line 10).
Regarding claim 18, Meyers et al. teaches the method of forming a photoresist layer, as explained above under claim 1, with use of a basic developer, tetramethyl ammonium hydroxide (TMAH) (column 23, lines 25-26) and exposing the wafer to EUV light (example 2, column 27, lines 49-50, and Fig. 7).
However, Meyers et al. is silent on the oxygen-containing environment of the post anneal process comprising NO2 or NO (claims 1, 13, and 18).
Paz de Araujo et al. is analogous to the instant application because Paz de Araujo et al. teaches a method of forming a film on a substate surface utilizing vapor deposition comprising a metal precursor gas and an oxidant gas to form a metal-oxo containing final material, similarly to the instant application. Paz de Araujo et al. teaches a method of fabricating a film of correlated electron materials (CEMs) (abstract) by an atomic layer deposition process utilizing precursors in a gaseous form [0051] such as AX and BY of expression (6) [0040] wherein “A” corresponds to a transition metal, transition metal oxide, or any combination thereof, such as tin [0040]; “X” corresponds to a ligand, such as organic ligand; and “BY” corresponds to an oxidizer such as oxygen (O2), ozone (O3), nitric oxide (NO), hydrogen peroxide (H2O2), just to name a few examples [0040-0042].
Further, Paz de Araujo et al. teaches several methods which are simplified into 3 flow charts as shown in Figs. 2A-2C. In particular, Fig. 2B shows a simplified flowchart for a method for fabricating correlated electron device materials, according to an embodiment 202, [0047] using a vapor deposition method to expose a substrate to precursor AX and BY under conditions of pressure and temperature to promote the formation of AB, a metal-oxo containing material [0054]. Figs. 6A-6C show the temperature profiles as a function of time used in the deposition and annealing processes for the method described above [0064] wherein the annealing may be performed in a temperature range from 20.0° C to 900.0° C (claim 3) and in a gaseous environment comprising one or more gasses such as oxygen (O2), water (H2O), nitric oxide (NO), nitrogen dioxide (NO2), ozone (O3), or carbon monoxide (CO) [0065] (claims 1 and 13). Furthermore, the deposition method is taught to be either a chemical vapor deposition, physical vapor deposition, sputter, plasma enhanced chemical vapor deposition or other methods of deposition or combinations of deposition methods such as a combination of ALD and CVD [0064] (claims 5, 7, and 13).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have combined the method of Meyers et al. with the method of Paz de Araujo et al. because the annealing process “improv[es] the film properties, performance or endurance…such as reduce resistance variations” [0057]. See MPEP § 2143, rationales (A and B). See also KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385, 1395-97 (2007).
Regarding claim 3, Meyers et al. further teaches “using the precursor solutions described herein, some hydrolysis and condensation generally is performed during coating, and may be completed or furthered post coating via subsequent processing steps such as heating in air” (column 15, lines 46-50) wherein the temperature range of the heating is “from about 45° C to about 250° C”(column 17, lines 51-52). The range of 45-250° C in Meyers et al. overlaps with the claimed range of 25-250° C. Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping range of 45-250 ° C, as the disclosed by Meyers et al., because selection of overlapping portion of ranges has been held to be a prima facie case of obviousness. See MPEP § 2144.05.I. In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66 (Fed. Cir. 1997).
Regarding claims 6, 8, 16, and 19 Meyers et al. teaches the method of claim 5, as explained above, and that the metal precursor can be “a range of RnSnX(4-n) compounds where n= 0, 1, or 2” (column 19, line 7) and further gives several examples similar to the claimed compound such as (C6H5)CH2Sn(NMe2)3 (column 19, lines 22-23). Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected a similar compound to PhSn(NMe2)3, such as (C6H5)CH2Sn(NMe2)3, because chemical compounds having very close structural similarities and similar utilities has been held to be a prima facie case of obviousness. See MPEP 2144.09(I) and In re Payne, 606 F.2d 303, 313, 203 USPQ 245, 254 (CCPA 1979).
Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1) as applied to claim 3 and explained above, and in further view of Chandra et al. (WO 2016126911 A2).
Regarding claim 4, Meyers et al. in view of Paz de Araujo et al. teaches the post anneal method of claim 3, as explained above. However, Meyers et al. in view of Paz de Araujo et al. is silent on the post anneal process performed at a pressure less than 200 torr (claim 4).
Chandra et al. teaches compositions and methods for forming a silicon-containing film using a vapor deposition method (such as CVD or ALD) [35] followed by an annealing such as an oxygen annealing [62]. Chandra et al. is analogous to the instant application because both teach a vapor deposition method followed by an annealing process in an oxygen environment, as in instant claim 1. Chandra et al. teaches “oxygen annealing was performed at 2 Torr” [8].
Modifying the post anneal method taught by Meyers et al. in view of Paz de Araujo et al. with the post anneal pressure teachings of Chandra et al. would have been obvious to one skilled in the art at the time of filing, as all 3 prior art references teach methods of post anneal under an oxygen environment, therefore, the results of the combination would have been predictable. See MPEP § 2143(I)(A) and KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385,1395-97 (2007). Further, the pressure of 2 torr in Chandra et al. overlaps with the claimed pressure of less than 200 torr. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping range of 2 torr as disclosed by Chandra et al. because selection of overlapping portion of ranges has been held to be a prima facie case of obviousness. See MPEP § 2144.05.I. In re Geisler, 116 F.3d 1465, 1469-71, 43 USPQ2d 1362, 1365-66 (Fed. Cir. 1997).
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1) as applied to claim 1 and explained above, and in further view of Smith et al. (US 20180012759 A1).
Regarding claim 10, Meyers et al. in view of Paz de Araujo et al. teaches the method of claim 1, as explained above. However, Meyers et al. in view of Paz de Araujo et al. are silent on the CVD process not being a condensation process.
Smith et al. is analogous to the instant application as both teach depositing a metal oxide atop of a substrate using a vapor deposition process, such as ALD or CVD. Smith et al. teaches depositing a tin oxide film atop of a semiconductor substrate using a vapor deposition method such as ALD or CVD, and further, teaches a CVD process that is not a condensation process [35].
Meyers et al. teaches an embodiment of reacting the precursor vapors at temperatures below about 200° C to prevent excessive condensation (column 19, lines 60-63). Modifying the method of Meyers et al. in view of Paz de Araujo et al. with the teachings of Smith et al. to include the CVD process without the use of condensation would have been obvious to one skilled in the art because “the temperature and pressure are selected such that the reactants remain in the gaseous form in the process chamber to avoid condensation” [35]. See MPEP § 2143(I)(A) and KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385,1395-97 (2007).
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1) as applied to claim 1 and explained above, and in further view of Wu et al. (WO 2019217749 A1).
Regarding claim 12, Meyers et al. in view of Paz de Araujo et al. teaches the formation of a positive tone photoresist layer on the surface of the substrate, as explained above in claim 1, the method of claim 11 where the CVD process is a condensation process, and Meyers et al. further teaches “the substrate and/or chamber and/or vapors may be heated to promote reaction and deposition on the substrate surface” (column 19, lines 58-60). However, Meyers et al. in view of Paz de Araujo et al. is silent on the metal precursor vapor being provided into the vacuum chamber from an ampoule maintained at a first temperature and the substrate is maintained at a second temperature less than the first temperature during the formation of the photoresist layer (claim 12).
Wu et al. teaches methods for making thin-films on semiconductor substrates comprising of mixing a vapor stream of an organometallic precursor with a vapor stream of a counter-reactant to form an organometallic material on the surface of a substrate using a vapor deposition method (abstract). Wu et al. further teaches the CVD process is a condensation process “the product from such vapor-phase reaction… is then condensed or otherwise deposited onto the substrate” [0024] and “the temperature of the substrate is preferably…below the temperature of the reactant streams” [0025], wherein the “reactant streams” include “a vapor stream of an organometallic precursor” [0023]. The term “reactant streams” are synonymous with the claim language of “ampoule” as they serve the same purpose of being a vessel for holding the metal precursor at a temperature higher than the substrate before adding the metal precursor vapor into the chamber.
Modifying the method of Meyers et al. in view of Paz de Araujo et al. with the teachings of Wu et al. to include a difference in temperature between the metal precursor vapor and substrate would have been obvious to one skilled in the art, as both references teach similar CVD processes which proceeds through condensing the product onto the substrate. One of ordinary skill in the art would have combined the elements from Meyers et al. in view of Paz de Araujo et al. and Wu et al. to achieve the same function as the individual functions of each element and the results of the combination would be predictable. See MPEP § 2143(I)(A) and KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385,1395-97 (2007).
Claims 14-15 are rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1) as applied to claim 13 and explained above, and in further view of Smith et al. (US 20180012759 A1).
Regarding claims 14 and 15, Meyers et al. in view of Paz de Araujo et al. teaches the method of claim 13, as explained above, and Meyers et al. further teaches that “the pressure and temperature in the reaction chamber can be selected to control the reaction process” (column 18, lines 56-58). However, Meyers et al. in view of Paz de Araujo et al. fails to explicitly teach thermal (claim 14) or plasma enhanced (claim 15) ALD.
Smith et al. is analogous to the instant application as both teach depositing a metal oxide atop of a substrate using a vapor deposition process. Smith et al. teaches depositing a tin oxide film atop of a semiconductor substrate using a vapor deposition method such as ALD or CVD. Regarding claims 14 and 15, Smith et al. teaches “thermal or plasma enhanced ALD can be used” [35].
Modifying the method of Meyers et al. in view of Paz de Araujo et al. with the ALD deposition of Smith et al. would have been obvious to one skilled in the art, as both methods teach an ALD process and heating the vapor deposition chamber “promote(s) reaction and deposition on the substrate” (Meyers et al., column 19, lines 58-59) or the use of plasma to “enhance the reaction rate” (Smith et al., [39]). One of ordinary skill in the art could have combined the elements from Meyers et al. in view of Paz de Araujo et al. and Smith et al. to achieve the same function as the individual functions of each element and the results of the combination would be predictable. See MPEP § 2143(I)(A) and KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385,1395-97 (2007).
Claims 9, 17, and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Meyers et al. (US 10,228,618 B2) in view of Paz de Araujo et al. (US 20170213961 A1) as applied to claims 7, 13 and 18, respectively, and in further view of Lui et al. (US 8377816 B2).
Regarding claims 9, 17, and 20, Meyers et al. in view of Paz de Araujo et al. teaches the method of claim 7, 13, and 18, respectively, as explained above. Meyers et al. further teaches that the metal precursor can be “a range of RnSnX(4-n) compounds where n= 0, 1, or 2” (column 19, line 7) and gives an example similar to the claimed compound, Sn(OtBu)4 (column 19, line 32). However, Meyers et al. in view of Paz de Araujo et al. fails to explicitly teach Sn(nBu)4.
Lui et al. is analogous to the instant application as both utilize CVD as the process of depositing a tin-based precursor vapor onto a surface. Lui et al. teaches forming a protection layer atop a surface using CVD with the gaseous precursor being a tin complex such as Sn(nBu)4 and the use of “tetrabutyl tin (Sn(nBu)4)” as a “gaseous precursor” (column 3, lines 24-25), where “gaseous precursor” is synonymous with “precursor vapor”.
Modifying the method of Meyers et al. in view of Paz de Araujo et al. with the tin complex of Lui et al. would have been obvious to one skilled in the art, as both methods teach the metal precursor to be tin-based, such as with a general compound structure of RnSnX(4-n) in Meyers et al., for use in a vapor deposition method such as CVD. See MPEP § 2143(I)(A) and KSR Int'l Co. v. Teleflex Inc., 550 U.S. 398, 415-421, 82 USPQ2d 1385,1395-97 (2007). Further, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected a compound with similar structure, such as Sn(OtBu)4 in Meyers et al., because chemical compounds having very close structural similarities and similar utilities has been held to be a prima facie case of obviousness. See MPEP 2144.09(I) and In re Payne, 606 F.2d 303, 313, 203 USPQ 245, 254 (CCPA 1979).
Conclusion
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/CHRISTINE CURIAC/Examiner, Art Unit 1737
/MARK F. HUFF/Supervisory Patent Examiner, Art Unit 1737
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